Reference is also made to commonly-owned copending Ser. No. 09/442,025, filed Nov. 17, 1999; Ser. No. 09/451,319, filed Nov. 30, 1999; Ser. No. 09/451,344, filed Nov. 30, 1999; Ser. No. 09/456,781, filed Dec. 8, 1999; Ser. No. 09/663,788, filed Sep. 18, 2000; Ser. No. 09/663,948, filed Sep. 18, 2000; Ser. No. 09/732,601, filed Dec. 7, 2000; and Ser. No. 09/785,890, filed Feb. 16, 2001. The entire disclosures of each of the foregoing eight (8) applications to the extent not in conflict with the present application, are incorporated herein by reference. Reference is also made to commonly-owned copending application No. 09/296,499, filed Apr. 22, 1999, now U.S. Pat. No. 6,110,387, issued Aug. 29, 2000; and Ser. No. 09/658,839, filed Sep. 8, 2000.
Bromine-based biocides have proven biocidal advantages over chlorination-dechlorination for the microbiological control of cooling waters and disinfection of waste treatment systems. The water treatment industry recognizes these advantages to be cost-effective control at higher pH values, almost no loss in biocidal activity in the presence of ammonia, and effective control of bacteria, algae and mollusks.
A common way of introducing bromine based biocides into a water system is through the use of aqueous NaBr in conjunction with NaOCl bleach. The user feeds both materials to a common point whereupon the NaOCl oxidizes the bromide ion to HOBr/OBrxe2x8ax96. This activated solution is then introduced directly into the water system to be treated. The feeding of the two liquids in this fashion is necessary because the HOBr/OBrxe2x8ax96 mixture is unstable and has to be generated on-site just prior to its introduction to the water. Furthermore, the feeding, and metering of two liquids is cumbersome, especially as the system has to be designed to allow time for the activation of bromide ion to occur. Consequently many biocide users have expressed the need for a single-feed, bromine-based biocide. Elemental bromine and molecular bromine chloride have been considered to meet these demands. Both are liquids at room temperature and can be fed directly to the water system, where immediate hydrolysis occurs to yield HOBr.
Br2+H2Oxe2x86x92HOBr+HBrxe2x80x83xe2x80x83(1) 
BrCl+H2Oxe2x86x92HOBr+HClxe2x80x83xe2x80x83(2) 
Properties of bromine and bromine chloride are compared in Table 1.
It can be seen that certain characteristics of these materialsxe2x80x94especially their corrosiveness, high vapor pressures and fuming tendenciesxe2x80x94necessitate care and skill in their handling and use. Early efforts to overcome the deficiencies of these materials comprised complexing bromine with excess bromide ion in the presence of strong acid and stabilizing the resultant solutions with ethanolamine. The resultant solutions of ethanolammonium hydrogen perbromide contained up to 38% by weight elemental bromine. See in this connection, Favstritsky, U.S. Pat. No. 4,886,915; and Favstritsky, Hein, and Squires, U.S. Pat. No. 4,966,716.
These solutions permitted introduction of bromine to a water system using a single feed. As in the case of bromine and bromine chloride, the ethanolammonium hydrogen perbromide hydrolyzed in water to release HOBr. The vapor pressures of these solutions were lower than elemental bromine and bromine chloride. Nevertheless, the solutions still possessed measurable vapor pressures, and thus tended to produce undesirable reddish-colored vapors during storage and use. An economically acceptable way of stabilizing high concentrations of aqueous solutions of bromine chloride is described in U.S. Pat. No. 5,141,652 to Moore, et al. The solution is prepared from bromine chloride, water and a halide salt or hydrohalic acid. These solutions were found to decompose at a rate of less than 30% per year and in cases of high halide salt concentration, less than 5% per year. Moreover, solutions containing the equivalent of 15% elemental bromine could be prepared. Unfortunately, the relatively high acidity of these solutions and their tendency to be corrosive and fuming impose limitations on their commercial acceptance.
Many solid bromine derivatives such as BCDMH (1,3-bromochloro-5,5-dimethylhydantoin) are limited in the amount of material that can be dissolved in water and fed as a liquid to the water treatment system. For example, the solubility of BCDMH in water is only around 0.15%. Another limitation of such derivatives is that at neutral pH, HOBr rapidly decomposes, eventually forming bromide ions. Thus, the ability to store and transport these aqueous solutions is greatly limited and of questionable commercial feasibility.
U.S. Pat. No. 3,558,503 to Goodenough et al. describes certain aqueous bromine solutions stabilized with various stabilizing agents and various uses to which such solutions can be put. The compositions described in the patent comprise an aqueous bromine solution having from about 0.01 to about 100,000 parts per million by weight of bromine values wherein the molar ratio of bromine to nitrogen present in the bromine stabilizer ranges from about 2.0 to 1 to about 0.5 to 1. The stabilizer used is biuret, succinimide, urea, a lower aliphatic mono- or disubstituted urea containing from about 2 to about 4 carbon atoms in each substituent group, sulfamic acid, or an alkyl sulfonamide of the formula RSO3NH2 where R is a methyl or ethyl group. The solution also contains sufficient hydroxide additive to provide a pH in the solution ranging from about 8 to about 10, the hydroxide additive being an alkaline earth hydroxide or an alkali metal hydroxide.
U.S. Pat. No. 5,683,654 to Dallmier et al. discusses the preparation of aqueous alkali metal or alkaline earth metal hypobromite solutions by mixing an aqueous solution of alkali or alkaline earth metal hypochlorite with a water soluble bromide ion source to form a solution of unstabilized alkali or alkaline earth metal hypochlorite. To this solution is added an aqueous solution of an alkali metal sulfamate having a temperature of at least 50xc2x0 C. and in an amount that provides a molar ratio of alkali metal sulfamate to alkali or alkaline earth metal hypobromite of from about 0.5 to about 6 whereby a stabilized aqueous alkali or alkaline earth metal hypobromite solution is formed. The Dallmier et al. patent teaches that much higher levels of available halogen for disinfection were attained by this approach as compared to the Goodenough et al. approach. But the Dallmier et al. patent acknowledges that in their process, the stabilization must occur quickly after the unstable NaOBr is formed.
This invention involves a new process of forming concentrated aqueous solutions of biocidally active bromine and in so doing, provides novel and eminently useful concentrated aqueous biocidal solutions of bromine and bromine chloride. Such concentrated solutions can be stored and shipped, and they serve as articles of commerce which, in use, are mixed into the water to be treated for microbiological control. The concentrated aqueous biocidal solutions of this invention are also useful in combating biofilms on surfaces contacted by water. Thus when put to use for microbiological control or biofilm eradication, the concentrated biocidal solutions of this invention are normally diluted in the water being treated. However, in severe cases it is possible to apply a concentrated solution of this invention directly onto a surface infested with biofilm and/or other microbial species or pathogens.
In one of its embodiments this invention provides a process of producing a concentrated liquid biocide composition which comprises mixing (a) bromine chloride or bromine with (b) an aqueous solution of alkali metal salt of sulfamic acid (preferably the sodium salt), the solution having a pH of at least about 7, e.g., in the range of about 10 to about 13.5, and preferably in the range of about 12.5 to about 13.5. The amounts of (a) and (b) used are such that (i) the content of active bromine in the concentrated solution is at least 100,000 ppm (wt/wt) and (ii) the atom ratio of nitrogen to active bromine from (a) and (b) is greater than 1 when bromine is used, and greater than 0.93 when bromine chloride is used. It is preferred that the content of active bromine in the concentrated solution is in the range of from about 145,000 ppm to about 160,000 ppm. It is also preferred, to utilize an atom ratio of nitrogen to active bromine from (a) and (b) that is greater than 1 even when using bromine chloride in the process. In a preferred embodiment the aqueous solution of alkali metal salt of sulfamic acid used in the process is preformed by mixing together in water, (i) sulfamic acid and/or an alkali metal salt of sulfamic acid, and (ii) alkali metal base in proportions such that an aqueous solution of alkali metal salt of sulfamic acid is formed having a pH of at least 7, e.g., in the range of 10 to about 12 or 12.5, and preferably in the range of about 12.5 to about 13.5. If sulfamic acid itself is used as the starting material, it is used initially as a slurry in water with which the alkali metal base is mixed.
When introducing the bromine chloride or bromine into the aqueous solution of alkali metal salt of sulfamic acid, it is desirable to maintain the desired pH of the resulting solution at 7 or above by also introducing into the solution (continuously or intermittently, as desired) additional alkali metal base, such as by a co-feed of an aqueous solution of alkali metal base. When the concentrated aqueous solution is to be stored in drums, it is desirable to have the pH of such solution at about 10 or above, and preferably in the range of about 12.5 to about 13.5.
It is preferred to employ bromine chloride as the source of the active bromine in the above process because in the resulting aqueous compositions, all of the bromine of the bromine chloride is made available as active bromine capable of providing biocidal activity in solution. In other words, the chlorine of the bromine chloride is converted in the process to dissolved alkali metal chloride salt, thereby liberating the bromine as the active bromine content of the biocidal composition which is capable of providing biocidal activity. Thus the more expensive component of the bromine chloridexe2x80x94viz., brominexe2x80x94is fully utilized in forming active bromine in the aqueous biocidal composition, and concurrently the less expensive componentxe2x80x94the anionic chlorine in the bromine chloridexe2x80x94makes this beneficial result possible.
The term xe2x80x9cactive brominexe2x80x9d of course refers to all bromine-containing species that are capable of biocidal activity. It is generally accepted in the art that all of the bromine in the +1 oxidation state is biocidally active and is thus included in the term xe2x80x9cactive brominexe2x80x9d. As is well known in the art, bromine, bromine chloride, hypobromous acid, hypobromite ion, hydrogen tribromide, tribromide ion, and organo-N-brominated compounds have bromine in the +1 oxidation state. Thus these, as well as other such species to the extent they are present, constitute the active bromine content of the compositions of this invention. See, for example, U.S. Pat. No. 4,382,799 and U.S. Pat. No. 5,679,239. A well-established method in the art for determining the amount of active bromine in a solution is starch-iodine titration, which determines all of the active bromine in a sample, regardless of what species may constitute the active bromine. The usefulness and accuracy of the classical starch-iodine method for quantitative determination of bromine and many other oxidizing agents has long been known, as witness Chapter XIV of Willard-Furman, Elementary Quantitative Analysis, Third Edition, D. Van Nostrand Company, Inc., New York, Copyright 1933, 1935, 1940.
A typical starch-iodine titration to determine active bromine is carried out as follows: A magnetic stirrer and 50 milliliters of glacial acetic acid are placed in an iodine flask. The sample (usually about 0.2-0.5 g) for which the active bromine is to be determined is weighed and added to the flask containing the acetic acid. Water (50 milliliters) and aqueous potassium iodide (15% (wt/wt); 25 milliliters) are then added to the flask. The flask is stoppered using a water seal. The solution is then stirred for fifteen minutes, after which the flask is unstoppered and the stopper and seal area are rinsed into the flask with water. An automatic buret (Metrohm Limited) is filled with 0.1 normal sodium thiosulfate. The solution in the iodine flask is titrated with the 0.1 normal sodium thiosulfate; when a faint yellow color is observed, one milliliter of a 1 wt % starch solution in water is added, changing the color of the solution in the flask from faint yellow to blue. Titration with sodium thiosulfate continues until the blue color disappears. The amount of active bromine is calculated using the weight of the sample and the volume of sodium thiosulfate solution titrated. Thus, the amount of active bromine in a composition of this invention, regardless of actual chemical form, can be quantitatively determined.
By utilizing bromine or bromine chloride with caustic in the stabilized bromine composition, higher levels of active halogen are achievable, compared to the levels obtained by the addition of sodium hypochlorite to sodium bromide. The process and the compositions formed also have about twice the content of active bromine as the most concentrated solutions produced pursuant to the Goodenough, et al. patent. Moreover, even at the high levels of active bromine that exist in the compositions of this invention, it has been found possible to provide biocidal compositions that maintain these high levels of active bromine for at least a two-month period, and that do not exhibit a visible or offensive vapor or odor during this period.
In another embodiment, alkali metal dichlorohypobromite, M[BrCl2] (M=alkali metal) is preformed by pre-mixing bromine chloride with aqueous sodium chloride, and the bromine chloride is used in this form to provide the active bromine content of the resultant solution. The preferred alkali metal dichlorohypobromite is sodium dichlorohypobromite.
Another embodiment of this invention is an aqueous biocide composition comprising water having in solution therein (i) an active bromine content derived from bromine chloride of at least about 100,000 ppm (wt/wt), (ii) an alkali metal salt of sulfamic acid (preferably the sodium salt), and (iii) an alkali metal chloride (preferably sodium chloride), wherein the relative proportions of (i) and (ii) are such that the atom ratio of nitrogen to active bromine is greater than 1, and wherein the pH of the composition is at least 7, e.g., in the range of 10 to about 13.5, and preferably in the range of about 12.5 to about 13.5. It is preferred that the content of active bromine in the solution is in the range of from about 145,000 ppm to about 160,000 ppm. In a less preferred embodiment (i) is bromine (Br2) and (iii) is an alkali metal bromide (especially sodium bromide).
The preferred way of forming the above aqueous biocide compositions comprising water having in solution therein an active bromine content of at least about 100,000 ppm (wt/wt), and preferably from about 145,000 ppm to about 160,000 ppm (wt/wt) is to mix together (i) bromine chloride, and (ii) an aqueous solution of alkali metal salt of sulfamic acid, or (iii) water and an alkali metal salt of sulfamic acid, or (iv) water, an alkali metal base, and sulfamic acid, or (v) any combination of (ii), (iii), and (iv), and in relative proportions of such that the atom ratio of nitrogen to active bromine in said biocide composition is greater than 0.93, preferably greater than 1, and the pH of the biocide composition is at least 7 (e.g., in the range of about 10 to about 13.5), and preferably in the range of about 12 or 12.5 to about 13.5.
This invention has made it possible to provide an aqueous biocide composition having a pH of at least 7 and that comprises water having in solution (i) an active bromine content of at least about 100,000 ppm (wt/wt), and (ii) an atom ratio of nitrogen to active bromine of greater than 0.93, the nitrogen originating from sulfamic acid and/or an alkali metal salt thereof, and in which the composition (a) is devoid or essentially devoid of bromate, and (b) since its inception has been devoid or essentially devoid of bromate. By xe2x80x9cdevoidxe2x80x9d of bromate is meant that using the test procedure described hereinafter the level of bromate, if any, is below a detectable amount. Similarly, by xe2x80x9cessentially devoidxe2x80x9d of bromate is meant that using the test procedure described hereinafter the presence of bromate is confirmed, but that the amount thereof is not more than 50 ppm (wt/wt).
In each of the embodiments of this invention, the atom ratio of nitrogen to active bromine is preferably in the range of about 1.1 to about 1.5, and more preferably in the range of from about 1.35 to about 1.5. Still higher ratios can be employed, if desired.
A further embodiment of this invention is a composition comprising an aqueous solution containing a stable oxidizing bromine compoundxe2x80x94i.e., a stabilized active bromine contentxe2x80x94wherein the solution is free of detectable bromate. Preferably such composition from its inception is free of detectable amounts of bromate, or in other words, the solution contains at all times from its inception less than 50 ppm of bromate. The stabilized active bromine content of the compositions of this embodiment can be derived from bromine and sulfamic acid or an alkali metal sulfamate such as sodium sulfamate or potassium sulfamate. However, most preferably the stable oxidizing bromine compound is of the type obtainable from bromine or from a combination of bromine and chlorine such as for example, bromine chloride or a mixture of bromine chloride and bromine, and sulfamic acid or an alkali metal sulfamate such as sodium sulfamate. When in the form of a concentrated solution, these compositions contain at least 100,000 ppm (wt/wt), i.e., at least 10 wt %, based on the total weight of the aqueous solution, and most preferably at least about 145,000 ppm (e.g., in the range of about 145,000 to about 160,000 ppm (wt/wt) of active bromine content. Amounts above 160,000 ppm (wt/wt) are also within the scope of this invention. In other words, any concentration of the stabilized active bromine component(s) above about 160,000 ppm (wt/wt) that does not result in precipitate formation during storage or transportation of the concentrated solution under normal ambient temperature conditions constitute compositions of this invention. When used for microbiological control, the concentrated solutions of this invention are mixed or diluted with, or introduced into, additional water, which typically is the water being treated for such microbiological control, so that the amount of active bromine in the water being treated for microbiological control is a microbiologically effective amount. The various compositions of the embodiments referred to in this paragraph preferably additionally contain dissolved chloride ion, most preferably in the presence of a stoichiometric excess of alkali metal cation, such as sodium or potassium cations. In contrast to certain other alkali metal salts, the alkali metal chloride salts have high solubilities in the aqueous medium of the concentrates of this invention, and thus pose no problem with respect to precipitate formation during storage, transportation, or use. In addition, the dissolved alkali metal chloride in the solutions of this invention minimize the extent to which oxygen or air becomes dissolved in the concentrated solutions.
Although not mandatory, it is preferred that from the inception of their production the compositions of this invention are and remain at all times free of peroxides.
Still other embodiments of this invention include the following:
1) A concentrated biocidal composition containing sulfamate-stabilized bromonium ion, such composition (i) from its inception, having a pH in excess of 8 and (ii) having greater than about 10 wt % bromonium ion present, measured as Br2, such wt % being based on the total weight of the composition.
2) A concentrated biocidal composition containing sulfamate-stabilized bromonium ion, such composition (i) containing up to about 16 wt % bromonium ion, measured as Br2, such wt % being based upon the total weight of the composition, (ii) from its inception, being free of detectable amounts of bromate ion, and (iii) from its inception, having a pH greater than 10.
3) A concentrated biocidal composition containing sulfamate-stabilized bromonium ion, such composition (i) containing at least about 10 wt % bromonium ion, measured as Br2, such wt % being based upon the total weight of the composition, (ii) having a pH greater than 10 and (iii) containing no detectable bromate ion.
4) A concentrated biocidal composition containing stabilized oxidizing halogen obtained by the reaction of BrCl and xe2x8ax96SO3NH2, such composition (i) having up to 16 wt % bromonium ion, measured as Br2, such wt % being based upon the total weight of the composition, and (ii) having a pH greater than 10.
5) A concentrated biocidal composition containing stabilized oxidizing halogen obtained by the reaction of BrCl and xe2x8ax96SO3NH2, such composition having a pH greater than 10.
6) A concentrated biocidal composition containing stabilized oxidizing halogen obtained by the reaction of BrCl and xe2x8ax96SO3NH2, such composition containing at least about 10 wt % bromonium ion, measured as Br2, such wt % being based upon the total weight of the composition.
7) A concentrated biocidal composition containing at least about 10 wt % xe2x8ax96SO3NH2 stabilized non-BrOxe2x8ax96-oxidizing halogen.
8) A concentrated biocidal composition containing stabilized non-BrOxe2x8ax96-oxidizing halogen, such composition having a pH greater than 10.
9) An aqueous mixture containing stabilized oxidizing halogen and having a pH between about 7 and about 8.
Preferably, but not necessarily, the composition of 1), 2), 3), 7), 8), and 9) immediately above are further characterized by comprising chloride ion in solution therein.
In further embodiments, this invention provides methods for disinfecting surfaces and for sanitizing bodies of water using a bromine-based biocide of this invention. Examples of surfaces that may be disinfected using the methods of this invention include domestic, commercial, industrial, and governmental kitchen counters, tables, floors, and sinks; and bathroom counters, walls, fixtures, and floors. The bodies of water that may be sanitized using the methods of this invention include cooling water systems, waste water effluents, pulp and paper mills, oilfields, air washers, fire reservoirs, and evaporative condensers. These methods use concentrated liquid biocide compositions comprising a biocidally active bromine-based biocide of this invention.
The methods for disinfecting a surface comprise applying to the surface a liquid biocide formed by diluting a concentrate of this invention with an amount of additional water that still contains sufficient biocidally active bromine content to effectively challenge the microorganisms on the surfaces being contacted by the diluted solution. Preferably the diluted solution as applied to the surface contains at least a minimum biofilm eradication concentration (MBEC) of active bromine, which of course will vary somewhat depending upon the biofilm producing species being biocidally challenged. Typical dilutions and methods that can be used for determining MBEC are illustrated in Example 10 hereinafter.
Another embodiment of this invention provides a method of sanitizing a body of water which method comprises introducing into the body of water a liquid biocide composition of this invention. Typically the biocide composition is introduced in concentrated form as received into the body of water. However it is possible to partially dilute the concentrate and to introduce the partially diluted concentrate into the body of water. The amount of the biocide solution, whether used as the original concentrate or as a partially diluted solution formed therewith, should of course contain a sufficient biocidally active bromine content to effectively challenge the microorganisms that are in the body of water being treated and that are on the surfaces that are in contact with or contacted by the body of water being treated. This amount of treating solution used will largely depend on the volume of water being treated and the concentration of the biocide solution being introduced into the water, and to some extent upon the species of microorganisms being challenged. The treated body of water preferably is treated such that it contains at least a minimum inhibitory concentration (MIC) of active bromine. Methods that can be used for determining MIC are illustrated in Example 11 hereinafter.
The organisms that may be controlled using one of the appropriate methods of this invention described above include bacteria, fungi, slime, and mollusks. Advantages resulting from use of the above methods of this invention include the effectiveness of the biocide solutions used, and the facts that the concentrated liquid biocide compositions provided herein are readily dissolved in water, are non-acidic, and are noncorrosive. Moreover sulfamate-stabilized aqueous concentrates when properly prepared pursuant to this invention are devoid or essentially devoid of bromate ion, and preferably contain no detectable bromate ion.
The above and other embodiments of this invention will be still further apparent from the ensuing description and appended claims.
A preferred alkali metal salt of sulfamic acid, and a preferred alkali metal base used in forming such salt are, respectively, potassium sulfamate and a potassium base such as KOH. Most preferred are, respectively, sodium sulfamate, and a sodium base such as NaOH.
One desirable way of accomplishing the mixing of the reactants when producing the concentrated liquid biocide formulations of this invention comprises concurrently introducing (a) bromine chloride and (b) an aqueous solution of alkali metal salt of sulfamic acid into a reaction zone, such as a reactor or other reaction vessel, and having the pH of the resulting solution at least at 7 (e.g., in the range of about 10 to about 13.5), and preferably in the range of about 12 or 12.5 to about 13.5. As noted above, the proportions of (a) and (b) used are such that the active bromine content of the solution is at least about 100,000 ppm (wt/wt), and preferably in the range of about 105,000 to about 120,000 ppm (wt/wt). Concentrated solutions containing as much as from about 145,000 to about 160,000 ppm (wt/wt) can be made and are useful especially when relatively freshly made, but have been found to be less storage stable than desired. Generally speaking, concentrates containing between above about 120,000 and below about 145,000 ppm, have satisfactory storage stability, by not as much as those containing in the range of about 105,000 to about 120,000 ppm (wt/wt). In addition, the proportions of (a) and (b) used are such that all of these concentrates have an atom ratio of nitrogen to active bromine from (a) and (b) that is greater than 0.93, and preferably greater than 1.
A general procedure for preparing the compositions of this invention using sulfamic acid involves, as a first step, forming a slurry of sulfamic acid in water. Typically the pH of this slurry is below 1 pH unit. Sodium hydroxide at 50% concentration is then added until the solid is completely dissolved. Additional 50% NaOH is added until the desired pH is reached. Bromine or bromine chloride is then added at a rate to allow the bromine to dissolve and react with the sulfamic acid without forming a pool of halogen on the bottom of the reactor. On a laboratory scale, a convenient rate of addition is approximately two drops per second. Sodium hydroxide (e.g., 25% or 50%) is co-fed to the reactor to maintain the desired pH (e.g., in the range of 10 to about 13.5, preferably in the range of about 12 or 12.5 to about 13.5, and it may be possible to operate even at a pH in the range of 13.5 to 14. It has been found that stable solutions containing as much as 26% active bromine (11.5% on an active chlorine basis) can be prepared by the process of this invention.
One of the features of this invention is that aqueous biocide compositions are provided that, even though unpurified, are devoid or are essentially devoid of bromate. In other words, if any bromate is present, the amount thereof as determined by use of the test procedure described hereafter is such that the concentrated aqueous biocide compositions of this invention contain bromate in an amount of up to and including (i.e., no greater than) 50 ppm (wt/wt) based on the total weight of the concentrated aqueous biocidal composition. In fact, in preferred concentrated aqueous biocide compositions of this invention this bromate content is in the range of from 0 to about 40 ppm (wt/wt) as determined using such test procedure.
As is known in the art, bromate is a very undesirable component of aqueous systems. For example, U.S. Pat. No. 5,922,745 points out that in 1995 the United States Environmental Protection Agency published a paper identifying some health concerns relevant to bromate formation (G. Amy, et al., Water Supply, 1995, 13(1), 157), and that in the same year animal carcinogenesis was linked to the presence of low levels of bromate in drinking water (J. K. Falwell, and G. O""Neill, Water Supply, 1995, 13(1), 29). While some prior processing achieved reductions in the amount of bromate formed when producing stabilized aqueous bromine-containing biocides, there has remained a need for still further reductions in the amount of bromate present in such biocides. Pursuant to this invention, such further reductions have been made possible. Furthermore, because of this invention, it is now possible to form a concentrated aqueous biocide composition having an active bromine content of at least about 100,000 ppm (wt/wt), and preferably in the range of about 145,000 to about 160,000 ppm (wt/wt), which not only is devoid or essentially devoid of bromate, but which since its inception has been devoid or essentially devoid of bromate. Thus in all stages in the production, handling, storage, transportation, and use of such compositions there is a reduced possibility of exposure to bromate. So far as is known, it has not been possible to achieve such results prior to this invention. Moreover, the water treated pursuant to this invention by addition thereto of an effective biocidal amount of active bromine results in a substantial dilution since, in general, on a wt/wt basis dosages in the treated water in the range of about 0.5 to about 20 parts per million of bromine (expressed as Br2) and preferably in the range of about 4 to about 10 parts per million of bromine (expressed as Br2) in the aqueous medium being treated for biocidal and/or biofilm control will usually suffice. This in turn means that the very small amount of bromate, if any, present in the concentrated aqueous solution of this invention is sharply reduced by orders of magnitude in the water being treated while achieving the microbiological control for which the composition is being used.
Still another feature of this invention is that the invention has made it possible to form a concentrated aqueous biocide composition having an active bromine content of at least about 100,000 ppm (wt/wt), which not only is devoid or essentially devoid of bromate, but which, since its inception, has always had a pH of greater than 8, and preferably in the range of about 12 to about 13.5. Thus it is not necessary to first reduce pH during processing and thereafter to increase the pH of the product solution. Avoidance of such pH adjustments materially simplifies the operations involved in the production of the resultant concentrated aqueous biocide composition of this invention. In addition, when the composition has been maintained at a pH of at least 12 or 13, e.g., in the range of 12 to about 13.5, from its inception, the possibility of bromate formation caused by exposure of the composition to reduced pH is virtually eliminated.
A further advantage of this invention is that it is unnecessary to produce the concentrated aqueous biocide compositions of this invention by use of powerful oxidants such as ozone or peroxides, which are known to possess undesirable, and indeed, hazardous characteristics.
The analytical test procedure to be used for determining the concentration, if any, of bromate in the compositions of this invention is an ion chromatography procedure in which UV detection is employed. The equipment required for the conduct of this procedure is as follows:
a) Ion Chromatographxe2x80x94Dionex DX-500 or equivalent, equipped with a UV detector and auto sampler.
b) Data Acquisition and Analysis Devicexe2x80x94VAX MULTICHROM or equivalent chromatography data collection and processing system.
c) Ion Chromatographic Columnxe2x80x94Dionex IonPac AG9-HC guard column (p/n 051791) in-line with a Dionex IonPac AS9-HC column (p/n 051786).
d) Volumetric Pipettesxe2x80x94any standard type of suitable volume.
e) Autosampler Vialsxe2x80x941-mL with caps.
f) Volumetric Flasksxe2x80x94100-mL.
g) Syringexe2x80x945-cc plastic syringe.
h) Pretreatment Cartridgexe2x80x94OnGuard-H from Dionex (p/n 039596).
The chemicals required for use in the procedure are as follows:
a) Waterxe2x80x94Deionized water with a specific resistivity of 17.8 megohm-cm or greater.
b) Sodium Carbonatexe2x80x94xe2x80x9cBaker Analyzedxe2x80x9d(copyright) reagent grade or equivalent.
c) Sodium Bromatexe2x80x94xe2x80x9cBaker Analyzedxe2x80x9d(copyright) reagent grade or equivalent.
The conditions used for the ion chromatograph are as follows:
The eluent is prepared by dissolving 0.4770 gram of the sodium carbonate in 1 liter of the deionized water. These are mixed well and the solution is filtered through a 0.2 IC compatible filter to degas the solution. The concentrated bromate standard solution is prepared by weighing 0.1180 gramxc2x10.001 gram of the sodium bromate into a 100-mL volumetric flask and diluting to volume with deionized water. This produces a solution containing 1,000 micrograms per milliliter of bromate. This concentrated bromate solution should be made fresh at least weekly. The bromate working standard solution is prepared by pipetting 100-microliters of the concentrated bromate standard solution into a 100-mL volumetric flask and filling the flask to volume with deionized water. The solution is mixed well, and yields a standard concentration of 1.0 microgram per milliliter of bromate.
The detailed procedure used for conducting the analysis of an aqueous solution of this invention involves the following steps:
a) Weigh 0.25 gram of the sample solution into a 100-mL volumetric flask. Fill to volume with deionized water and mix well.
b) Flush the OnGuard cartridge with 2-mL of deionized water.
c) Load 5-mL of the sample into the syringe attached to the OnGuard cartridge, pass through at a flow rate of 2 milliliters per minute, and discard the first 3 milliliters. Collect into a 1-mL autosampler vial and cap for analysis.
d) Analyze the samples, making duplicate injections, using the Ion Chromatograph instrument conditions given above.
The calculations involved in the procedure are as follows:
a) Calibration Standard: For bromate, calculate a response factor as follows: R=A/C where R is the response factor, A is the average area counts (2 injections), and C is concentration in micrograms per milliliter (xcexcg/mL).
b) Samples: ppm bromate=A/(Rxc3x97W) where A is the average area of sample peak (2 injections), R is the response factor, and W is the weight of the sample in grams.
A method for disinfecting a surface pursuant to this invention comprises applying a concentrated or diluted liquid sulfamate-stabilized biocide composition of the bromine chloride and/or alkali metal dichlorohypobromite to the surface to be disinfected. The liquid biocide composition may be applied to the surface to be disinfected in various ways. The composition may be poured directly onto the surface, sprayed onto the surface, or poured, sprayed or soaked onto an applicator which is then brought into contact with the surface. Applicators include, but are not limited to, cloths, sponges, paper towels, and mops.
A method of sanitizing a body of water pursuant to this invention comprises introducing a concentrated, or partially diluted, liquid biocide composition of sulfamate-stabilized bromine chloride and/or alkali metal dichlorohypobromite into the body of water. A variety of methods may be used to introduce the concentrated liquid biocide composition to the body of water to be sanitized. The concentrated liquid biocide composition may be added directly to the body of water, either all at once or slowly over time, for example via a pump or feeder. In systems in which the water is circulated through an apparatus, the concentrated liquid biocide composition may be added to this apparatus.
The addition of the concentrated liquid biocide composition to the body of water to be sanitized preferably yields a concentration of biocide in the body of water such that in the range of from about 2 to about 10 milligrams per liter of total available halogen, expressed as Cl2, is present in the body of water. In a preferred embodiment, the concentrated liquid biocide composition is introduced into the body of water as required, such that in the range of from about 2 to about 10 milligrams per liter of total available halogen, expressed as Cl2, is maintained within the body of water. A more preferred amount of total available halogen, expressed as Cl2, in the body of water is from about 2 to about 5 milligrams per liter. These concentrations of total available halogen, expressed as Cl2, are ordinarily sufficient for sanitizing a body of water and for maintaining sanitization of a body of water.
This invention provides a process of producing a concentrated liquid biocide composition which comprises mixing (a) bromine chloride with (b) an aqueous solution of alkali metal salt of sulfamic acid (preferably the sodium salt), the proportions of these components being such that the resulting solution has a pH of at least about 7, and preferably in the range of about 12 or 12.5 to about 13.5 or more. Compositions with a pH above about 12 have good shelf-life especially when the active bromine content in the solution is in the range of about 105,000 to about 120,000 ppm (wt/wt), and the atom ratio of nitrogen to active bromine from (a) and (b) is in the range of about 0.93 to about 1.5. Even better properties are obtained with compositions having a pH in the range of about 13 to about 14, an active bromine content in the range of about 145,000 to about 160,000 ppm (wt/wt), and with the atom ratio of nitrogen to active bromine from (a) and (b) in the range of about 1.28 to about 1.54. Bromine chloride is believed to be an equilibrium mixture of bromine chloride molecules, bromine molecules and chlorine molecules.
In a preferred process for producing the concentrated liquid biocide composition, the aqueous solution of alkali metal salt of sulfamic acid used in the process is preformed by mixing together in water, (i) sulfamic acid and/or an alkali metal salt of sulfamic acid, and (ii) alkali metal base in proportions such that an aqueous solution of alkali metal salt of sulfamic acid is formed having a pH of at least 7. If sulfamic acid itself is used as the starting material, it is used initially as a slurry in water with which the alkali metal base is mixed. It is preferred that the alkali metal salt of sulfamic acid is the lithium, sodium, or potassium salt; more preferred are the sodium and potassium salts. Highly preferred as the alkali metal salt of sulfamic acid is the sodium salt.
When mixing the bromine chloride with the aqueous solution of alkali metal salt of sulfamic acid, it is desirable to maintain the desired pH of the resulting solution at 7 or above by also introducing into the solution (continuously or intermittently, as desired) additional alkali metal base, such as by a co-feed of an aqueous solution of alkali metal base.
The use of bromine chloride as the source of the active bromine in the above process is advantageous because in the resulting aqueous compositions, all or essentially all of the bromine of the bromine chloride is made available as active bromine in solution. In other words, the chlorine of the bromine chloride is converted in the process to dissolved alkali metal chloride salt, thereby liberating the bromine as the active bromine content of the biocidal composition. Thus the more expensive component of the bromine chloridexe2x80x94viz., brominexe2x80x94is fully utilized in forming active bromine in the aqueous biocidal composition, and concurrently the less expensive componentxe2x80x94the anionic chlorine in the bromine chloridexe2x80x94makes this beneficial result possible.
By utilizing bromine chloride with caustic in the composition, higher levels of active halogen are achievable compared to the levels obtained by the addition of sodium hypochlorite to sodium bromide. The process and the compositions formed also have about twice the content of active bromine as the most concentrated solutions produced pursuant to the Goodenough, et al. patent. Moreover, even at the high levels of active bromine that exist in the compositions used in this invention, it has been found possible to provide biocidal compositions that maintain these high levels of active bromine for at least a two month period, and that do not exhibit a visible or offensive vapor or odor during this period.
This invention also provides an aqueous biocide composition comprising water having in solution therein (i) an active bromine content derived from bromine chloride of at least about 100,000 ppm (wt/wt), (ii) an alkali metal salt of sulfamic acid, and (iii) an alkali metal chloride, wherein the relative proportions of (i) and (ii) are such that the atom ratio of nitrogen to active bromine in the resultant composition is greater than 1, and the pH of the composition is at least 7, and preferably in the range of about 12 or 12.5 to about 13.5 or more. Again, the preferred alkali metal salt of sulfamic acid is the lithium, sodium, or potassium salt; more preferably, it is the sodium or potassium salt; the most preferred alkali metal salt of sulfamic acid is the sodium salt. Similarly, the alkali metal chloride is preferably lithium chloride, sodium chloride, or potassium chloride; more preferably it is sodium chloride or potassium chloride. Highly preferred as the alkali metal chloride is sodium chloride. In a less preferred embodiment, (iii) is an alkali metal bromide, most preferably sodium bromide.
This invention further provides a process for producing alkali metal dichlorohypobromite, M[BrCl2] (M=alkali metal), which is preformed by pre-mixing bromine chloride with aqueous alkali metal chloride, and the bromine chloride is used in this form to provide the active bromine content of the biocidal composition. The alkali metal of the alkali metal dichlorohypobromite may be lithium, sodium, potassium, rubidium, or cesium; preferred are lithium, sodium, and potassium; more preferred are sodium and potassium. Sodium dichlorohypobromite is the most preferred alkali metal dichlorohypobromite. Dichlorohypobromite is also referred to in the art as dichlorobromate, bromide dichloride, and dichlorobromide.
To form the biocidal composition, the alkali metal dichlorohypobromite is mixed with an aqueous solution of an alkali metal salt of sulfamic acid which has a pH of at least 7. In the resultant biocidal composition, the atom ratio of nitrogen to active bromine is greater than 0.93. It is preferred that the atom ratio is greater than 1.
In each of the embodiments of this invention, the atom ratio of nitrogen to active bromine in the biocidal composition is preferably in the range of about 1.1 to about 1.5. Still higher ratios can be employed, if desired.
The following examples are presented for purposes of illustration and not limitation.
Various compositions were prepared and the active bromine content of the resultant compositions was determined analytically. The conditions used and results obtained (observations on odor and vapor, and initial contents of active bromine in the solutions) are summarized in Table 2.
The specific details for Examples 1-4 of Table 2 are given below. Example 5 illustrates the embodiment of the invention wherein an alkali metal dichlorohypobromite is utilized as the source of active bromine.